Monitoring the Thiol/Thiophenol Molecule-Modulated Plasmon-Mediated Silver Oxidation with Dark-Field Optical Microscopy.

Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts.

Charge Dispersion Strategy for High-Performance and Rain-Proof Triboelectric Nanogenerator.

Triboelectric nanogenerator (TENG) is becoming a sustainable and renewable way of energy harvesting and self-powered sensing because of low cost, simple structure, and high efficiency. However, the output current of existing TENGs is still low. It is proposed that the output current of TENGs can be dramatically improved if the triboelectric charges can distribute inside the triboelectric layers. Herein, a novel single-electrode conductive network-based TENG (CN-TENG) is developed by introducing a conductive network of multiwalled carbon nanotubes in dielectric triboelectric layer of thermoplastic polyurethane (TPU). In this CN-TENG, the contact electrification-induced charges distribute on both the surface and interior of the dielectric TPU layer. Thus, the short-circuit current of CN-TENG improves for 100-fold, compared with that of traditional dielectric TENG. In addition, this CN-TENG, even without packing, can work stably in high-humidity environments and even in the rain, which is another main challenge for conventional TENGs due to charge leakage. Further, this CN-TENG is applied for the first time, to successfully distinguish conductive and dielectric materials. This work provides a new and effective strategy to fabricate TENGs with high output current and humidity-resistivity, greatly expanding their practical applications in energy harvesting, movement sensing, human-machine interaction, and so on.

Selective adsorption of cysteamine molecules on Au/TiO2 boosts visible light-driven photocatalytic hydrogen evolution.

Photocatalytic evolution of hydrogen is becoming a research hotspot because it can help to produce clean energy and reduce environmental pollution. Titanium dioxide (TiO2) and its composites are photocatalysts that are widely used in hydrogen evolution because of their high abundance in nature, low price, and high photo/chemical stability. However, their catalytic performances still need to be further improved, particularly in the visible light spectrum. Herein, visible light-driven photocatalytic evolution of hydrogen on Au/TiO2 nanocomposite is enhanced âˆ¼ 10 folds by selectively functionalizing the nanocomposite with cysteamine molecules. It is revealed that the amine group (-NH2) in cysteamine favors the transfer and separation of photo-generated hot carriers. The rate of hydrogen produced can be further tuned by varying the ionization of the functionalized molecules at different pH values. This work provides a simple, convenient, and effective method that can be used to improve the photocatalytic evolution of hydrogen. This method can also be used for many other nanocatalysts (e.g., Au-MoS2, Au-BiVO4) and catalytic reactions (e.g., carbon dioxide reduction, nitrogen reduction).

Density-of-States Matching-Induced Ultrahigh Current Density and High-Humidity Resistance in a Simply Structured Triboelectric Nanogenerator.

Triboelectric nanogenerators (TENGs) can covert mechanical energy into electricity in a clean and sustainable manner. However, traditional TENGs are mainly limited by the low output current, and thus their practical applications are still limited. Herein, a new type of TENG is developed by using conductive materials as the triboelectric layers and electrodes simultaneously. Because of the matched density of states between the two triboelectric layers, this simply structured device reaches an open-circuit voltage of 1400 V and an ultrahigh current density of 1333 mA m-2 when poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film and copper (Cu) or aluminum (Al) foil are used as the triboelectric pair. The current density increases by nearly three orders of magnitude compared with traditional TENGs. More importantly, this device can work stably in high-humidity environments, which is always a big challenge for traditional TENGs. Surprisingly, this TENG can even perform well in the presence of water droplets. This work provides a new and effective strategy for constructing high-performance TENGs, which can be used in many practical applications in the near future.

High-Performance Organic Electrochemical Transistor Based on Photo-annealed Plasmonic Gold Nanoparticle-Doped PEDOT:PSS.

Organic electrochemical transistors (OECTs), particularly the ones based on PEDOT:PSS, are excellent candidates for chemical and biological sensing because of their unique advantages. Improving the sensitivity and stability of OECTs is crucially important for practical applications. Herein, the transconductance of OECT is improved by 8-fold to 14.9 mS by doping the PEDOT:PSS channel with plasmonic gold nanoparticles (AuNPs) using a solution-based process followed by photo annealing. In addition, the OECT also possesses high flexibility and cyclic stability. It is revealed that the doping of AuNPs increases the conductivity of PEDOT:PSS and the photo annealing improves the crystallinity of the PEDOT:PSS channel and the interaction between AuNPs and PEDOT:PSS. These changes lead to the increase in transconductance and cyclic stability. The prepared OECTs are also demonstrated to be effective in sensitive detection of glucose within a wide concentration range of 10 nM-1 mM. Our OECTs based on photo-annealed plasmonic AuNP-doped PEDOT:PSS may find great applications in chemical and biological sensing, and this strategy may be extended to prepare many other high-performance OECT-based devices.

Preparation of Janus nanosheets composed of gold/palladium nanoparticles and reduced graphene oxide for highly efficient emulsion catalysis.

Interface/emulsion catalysis is an effective approach for many organic and inorganic chemical reactions. Positioning catalysts at the interface is essential for highly efficient interface/emulsion catalysis. The sheet-like Janus nanostructures may have great advantages in stabilizing emulsions and improving reaction efficiency. In this work, by using a simple emulsion reaction and photodeposition, we successfully prepare the Janus nanosheets with opposite sides composed of AuNPs/PdNPs and reduced graphene oxide (rGO) respectively, referred to as AuNP-rGO/PdNP-rGO Janus nanosheets. Due to the distinct hydrophilicities on opposite sides, the prepared Janus nanosheets demonstrate high efficiency in emulsion stabilization and emulsion catalysis. By introducing the prepared PdNP-rGO and AuNP-rGO Janus nanosheets in emulsion reactions, highly efficient hydrogenation of p-nitroanisole and photocatalytic degradation of Nile red are demonstrated. This work provides a simple and cost-effective method to prepare Janus nanosheets and realize highly efficient emulsion reactions, and this strategy can be extended to promote many other interface/emulsion reactions.